WO2015160668A1 - Modified vinylamine containing polymers and their use in papermaking - Google Patents
Modified vinylamine containing polymers and their use in papermaking Download PDFInfo
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- WO2015160668A1 WO2015160668A1 PCT/US2015/025406 US2015025406W WO2015160668A1 WO 2015160668 A1 WO2015160668 A1 WO 2015160668A1 US 2015025406 W US2015025406 W US 2015025406W WO 2015160668 A1 WO2015160668 A1 WO 2015160668A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/52—Amides or imides
- C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F220/56—Acrylamide; Methacrylamide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
- C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F271/00—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00
- C08F271/02—Macromolecular compounds obtained by polymerising monomers on to polymers of nitrogen-containing monomers as defined in group C08F26/00 on to polymers of monomers containing heterocyclic nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/12—Polymers provided for in subclasses C08C or C08F
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/44—Preparation of metal salts or ammonium salts
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/37—Polymers of unsaturated acids or derivatives thereof, e.g. polyacrylates
- D21H17/375—Poly(meth)acrylamide
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H17/00—Non-fibrous material added to the pulp, characterised by its constitution; Paper-impregnating material characterised by its constitution
- D21H17/20—Macromolecular organic compounds
- D21H17/33—Synthetic macromolecular compounds
- D21H17/34—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D21H17/41—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups
- D21H17/44—Synthetic macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing ionic groups cationic
- D21H17/45—Nitrogen-containing groups
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/06—Paper forming aids
- D21H21/10—Retention agents or drainage improvers
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/18—Reinforcing agents
Definitions
- compositions and methods of making the composition In particular graft copolymers of vinyl monomers and functionalized vinylamine-containing base polymers by Michael addition.
- the composition can be used alone or in combination with other additives for use in paper making and to improve paper making processes, drainage and paper dry strength properties.
- Functional polymers that are added as strength additives at the wet-end of the paper machine, especially in paper made from recycled fibers include amphoteric acrylamide based polymers and coacervate technology.
- amphoteric acrylamide based polymers and coacervate technology.
- An example of the former is described in US Patent No. 5,698,627, issued to Oguni, which teaches the synthesis of acrylamide based amphoteric copolymers that improve freeness, retention, and dry strength of recycled corrugated base paper.
- coacervate technology is described in US Patent No. 6,294,645. This wet-end dry strength system is comprised of a low charge
- polyamidoamine-epichlorohydrin and an anionic polyacrylamide added sequentially to pulp slurry.
- Polymers with amine functionality such as vinylamine based polymers derived from N-vinylformamide (VFA)
- VFA N-vinylformamide
- US Patent No. 2,721,140 discloses use of polyvinylamine as an additive to make papers having high wet strength
- US Patent No. 5,961,782 discloses the use of polyvinylamine to make crosslinked creping adhesive formulations.
- US Patent No. 4,421,602 discloses a partially hydrolyzed, water-soluble polymer of N-vinylformamide that contains N-vinylformamide units and vinylamine units. It also discloses use of polyvinylamine and a 50% hydrolyzed polyvuiylformamide to increase flocculation efficiencies, fines retention, and the drainage rate of pulp fiber in
- EP 0251182 discloses copolymers containing vinylamine and acrylonitrile units for use in papermaking as drainage aids, retention aids, as well as wet end additives for increasing the dry strength of paper products.
- Hofmann degradation of polyacrylamides is another approach to introduce primary amine functionality to polymers. Tanaka and Odberg, in J. Polym. Sci. Part A: Polymer Chemistry 1989, (27) 4329-4339, describes a method of preparing polyvinylamine via a Hofmann reaction of polyacryiamide.
- US Patent No. 5,039,757 discloses manufacturing of cationic polyacryiamide by Hofmann degradation process using polyacrylamides and its copolymers.
- US Patent Application No. 2010/186,914 Al and US Patent Application No.2010/326,614 Al disclose use of branched acrylamide copolymers and its subsequent Hofmann degradation to introduce primary amine functionality.
- use of hypohalogenite under alkaline conditions also results in hydrolysis of acrylamide functionality, and polymer degradation. Further purification of the polymer to remove residual hypohalogenite makes this approach expensive.
- Modification of vinylamine based polymers is another approach to introduce additional functionality to the polymer and alter its physical properties.
- US Patent No. 8,604,134 discloses modification of polyvinylamine with different functional groups and its application as paper making additive.
- US Patent No. 7,902,312 discloses Michael adduct of polyvinyl amine with ⁇ , ⁇ - unsaturated alkyl carbonyl compounds and its subsequent use as an additive for paper making system.
- US Patent No. 5, 994,449 discloses the use of vinylamine - vinyl alcohol copolymer functionalized with
- epichlorohydrin and its mixture with polyaminoamide as creping adhesive for paper application are epichlorohydrin and its mixture with polyaminoamide as creping adhesive for paper application.
- US patent application publication 2011/0155339 teaches a process for enhancing dry strength of paper by treatment with vinylamine-containing polymers and acrylamide- containing polymers.
- US 2011/0155339 describes a single-product blend that can react in aqueous solutions with primary amine groups in the vinylamine-containing polymer to form amide groups which may form a gelled or prohibitively high viscosity product which causes issues in papermaking.
- the present invention relates to a process of graft polymerization of vinyl monomer based on a functionalized vinylamine-containing polymer and compositions thereof. Such a graft polymerization results in a stable copolymer with essentially no added graft monomer on the functionalized vinylamine-containing polymer via Michael addition and provides a polymer of different chemical and physical properties compared with other linear polymers.
- the present invention relates to a composition of graft copolymers of vinyl monomers and functionalized vinylamine-containing base polymers by Michael addition.
- the present invention also relates to a process of making the graft copolymers.
- the resulting aqueous graft copolymers can be used as a cost effective paper making additive to improve paper making processes and paper dry strength properties.
- the present composition is also envisioned as being useful as a retention aid, deposit control and/or fixative agent, coagulant in paper making processes, flocculant in waste water treatment, plasticizers, viscosity modifier, personal care additive, coating material, slow releasing carriers for various industrial applications.
- This also relates to a functionalized vinylamine-containing polymer wherein the functionalized vinylamine polymer is obtained by Michael addition reaction with ⁇ , ⁇ - unsaturated alkyl carbonyl compounds such as ⁇ , ⁇ -unsaturated alkyl amides, esters and acids. These functionalized polymers are then subjected to free radically initiated graft polymerization (for more on graft polymerization see, for example,
- the amount of ⁇ , ⁇ - unsaturated alkyl carbonyl compounds, based on the vinylamine containing polymer can be from about 0.1 mole % to about 30 mole %, can be from about 0.2 mole % to about 20 mole %, can be fiom about 0.5 mole % to about 10 mole %, and may be in the range of from about 1 mole % to about 4 mole %.
- the molar ratio of functionalized vinylamine base polymer obtained via Michael addition to a vinyl monomer for graft polymerization can be varied from about 40:60 to about 80:20, can be from about 20:80 to about 60:40, can be from about 10:90 to about 50:50, and may be from about 5:95 to about 20:80.
- the graft copolymer described herein can be used, for example, to improve dry strength, wet strength, drainage, fixative, flocculation and sizing properties of paper when used as an additive in the papermaking process and has many other potential applications, such as, a retention aid, deposit control and/or fixative agent, coagulant in paper making processes, fiocculant in waste water treatment, plasticizers, viscosity modifiers, personal care additive, coating materials, slow releasing carriers for various industrial applications.
- the present invention relates to a graft copolymer composition of a vinyl monomer and a functionalized vinylamine-containing base polymer wherein the functionalized vinylamine-containing base polymer comprises randomly distributed repeating monomer units having the formula (I), (II) and (III),
- n, p and q are the numbers indicating mole % of the repeating units of formula (I), ( ⁇ ) and ( ⁇ ) present in the functionalized vinylamine- containing polymer; and wherein n can be from about 5 mole % to about 99 mole %, p can be from about 1 mole % to about 80 mole %, q can be from about 1 mole % to about 30 mole %; wherein the mole ratio of the functionalized vinylamine-containing polymer to the vinyl monomer in the graft polymer is in the range of from about 40:60 to about 80:20, can be from about 20:80 to about 60:40, can be from about 10:90 to about 50:50, and may be from about 5:95 to about 20:80.
- the ⁇ , ⁇ - unsaturated alkyl carbonyl compounds used to make functional ized vinylamine-containing polymer via Michael addition include, for example, acrylamide, methacrylamide, t-butyl acrylamide, N-alkylacrylamide, N- alkylmethacrylamide, N-[3-(propyl)trimethylammonium chloridejacrylamide, N-[3- (propyl)trimethylammonium chloride]methacrylamide, methyl acrylate, alkyl acrylate, methyl methacrylate, alkyl methacrylate, aryl acrylate, aryl methacrylates, [2- (methacryloyloxy)ethyl]-trimethylammonium chloride, N-[3-(dimethylamino)propyl] acrylamide, N-[3-(dimethylamino)propyl] methacrylamide, N-ethylacrylamide, 2- hydroxyethyl
- the vinyl monomer used in the current process can be acrylamide, acrylic acid, methacrylamide, methyl methacrylate, acrylonitrile, methyl acrylate, alkyl methacrylate, N-(2-methylpropanesulfonic acid)acrylamide, N-(glycolic acid)acrylamide, N-[3-(propyl)trimethylammonium chloridejacrylamide, and
- combinations thereof may be acrylamide, methacrylamide, methyl methacrylate and combinations thereof.
- the , ⁇ -unsaturated alkyl carbonyl compound is acrylamidopiOpyltrimethylammonium chloride and the vinyl monomer is acrylamide.
- the graft copolymer comprises a functionalized vinylamine-containing polymer that has repeating units of formula (I), (II) and (III) wherein n is from about 50 mole % to 100 mole %, p is from about 1 mole % to about 30 mole % and q is from about 1 mole % to about 15 mole %, the vinyl monomer is acrylamide, and the mole ratio of the functionalized vinylamine-containing polymer to acrylamide is from about 10:90 to about 50:50.
- formula (I), (II) and (III) wherein n is from about 50 mole % to 100 mole %, p is from about 1 mole % to about 30 mole % and q is from about 1 mole % to about 15 mole %, the vinyl monomer is acrylamide, and the mole ratio of the functionalized vinylamine-containing polymer to acrylamide is from about 10:90 to about 50:50.
- the graft copolymer comprises a functionalized vinylamine-containing polymer that comprises repeating units of formula (I), (II) and (III), wherein n is from about 80 mole % to 100 mole %, p is from about Imole % to about 15 mole % and q is from about 1 mole % to about 8 mole %, the vinyl monomer is acrylamide, wherein the mole ratio of the functionalized vinylamine-containing polymer to acrylamide is from about 5:95 to about 20:80.
- vinylamine repeating units in the vinylamine-containing polymer possess one primaiy amine and all of the vinylamine repeating units can theoretically be functionalized via Michael addition.
- too much functionalization of the vinylamine polymer can result in excess grafting and crosslinking of the graft copolymer.
- the graft copolymer of the present composition should have less than 30 mole% of the primaiy amine functionalized.
- the primary amine groups of the vinylamine repeating units on polyvinylamine are believed to be the active agents for wet strength. Functionalization of vinylamine- containing polymer via Michael addition can result in a decrease in primary amine content in the base polymer and also in the graft copolymer. For certain paper products, such as bath tissue, higher dry tensile and lower wet tensile properties are desirable.
- the amount of , ⁇ -unsaturated alkyl carbonyl compounds, based on vinylamine-containing polymer is less than about 30 mole %, can be less than 20 mole %, and may be less than 10 mole % to produce the Michael adduct.
- the ratio of the Michael adduct of the vinylamine-containing polymer to a vinyl monomer for graft polymerization can be varied from about 40:60 to about 80:20, can be from about 20:80 to about 60:40, can be from about 10:90 to about 50:50, and may be from about 5:95 to about 20:80.
- a process of preparing a composition through a free radically initiated graft polymerization of a vinyl monomer based on a functionalized vinylamine-containing base polymer comprises the step of (1) dissolving a functionalized vinylamine-containing polymer in a media, such as water, an ionized solution, a solvent or combinations thereof, (2) adjusting the pH to from about 1 to about 4, can be from about 2 to about 4, can be about 3.0 to about 3.8, and may be from about 3.2 to about 3.6, and (3) conducting free radical polymerization at a temperature of from about 30°C to about 100°C, can be from about 40°C to about 80°C, and may be from about 55°C to about 75°C, for from about 10 minutes to about 300 minutes, can be from about 30 minutes to about 150 minutes, and may be from about 40 minutes to about 80 minutes.
- free radical polymerization is conducted at a pH of from about 3.0 to about 3.8; at a temperature of from about
- the functionalized vinylamine-containing polymer is present in a reaction medium in an amount of from about 0.1% to about 20% active solids, can be from about 1% to about 15% active solids, can be from about 2% to about 10% active solids, and may be from about 3% to about 8% active solids.
- a method of making a graft copolymer composition using a vinylamine-containing base polymer wherein the base polymer comprises randomly distributed repeating monomer units having the formula (I) (II) and (III):
- R is a reacted , ⁇ - unsaturated alkyl carbonyl compound through Michael addition by vinylamine; n, p and q indicate the mole percent (mole %) of the repeating units of formula (I), (II) and/or (III) present in the functionalized polyvinylamine; wherein n is from about 5 mole % to about 99 mole %, p is from about 1 mole % to about 80 mole %, q can be from 0 mole % to about 30 mole %.
- initiators can be used in the current process to produce the graft copolymers of vinyl monomers and the functionalized vinylamine-containing base polymers, such as hydrogen peroxide, tert-butyl hydroperoxide (TBHP), sodium, potassium or ammonium persulfates, azo mitiators, and redox initiator systems.
- TBHP tert-butyl hydroperoxide
- sodium, potassium or ammonium persulfates sodium, potassium or ammonium persulfates
- azo mitiators azo mitiators
- redox initiator systems redox initiator systems.
- the initiator is hydrogen peroxide or tert-butyl hydroperoxide (TBHP).
- Another embodiment of the present invention is the aforementioned process with a proper selection of the initiator and polymerization temperature in combination, wherein said initiator is hydrogen peroxide, tert-butyl hydroperoxide, and sodium, potassium or ammonium persulfates, can be hydrogen peroxide, tert-butyl hydroperoxide, and may be hydrogen peroxide, wherein the temperature for the graft polymerization can be from about 40°C to about 90°C, can be from about 50°C to about 80°C, and may be from about 60°C to about 70°C.
- said initiator is hydrogen peroxide, tert-butyl hydroperoxide, and sodium, potassium or ammonium persulfates
- the temperature for the graft polymerization can be from about 40°C to about 90°C, can be from about 50°C to about 80°C, and may be from about 60°C to about 70°C.
- a hydrogen peroxide initiator is added to the aqueous medium and polymerization is carried out at a pH of from about 3.0 to about 3.8; at a temperature of from about 40°C to about 80°C for from about 40 minutes to about 80 minutes.
- the vinylamine-containing polymers used in the current process include, but is not limited to, partially or completely hydrolyzed poly(N- vinylformamide), copolymers of N-vinylformamide and vinyiamine, copolymers of vinyiamine and amidine, copolymers of N-vinylacetamide and vinyiamine, terpolymers of N-vinylformamide, vinyiamine and amidine, terpolymers of N-vinylfoi-mamide, vinyiamine and vinyiamine methyl chloride quaternary ammonium salts, terpolymers of N-vinylformamide, vinyiamine and vinyl alcohol, terpolymers of N-vinylformamide, vinyiamine and vinyl acetate, terpolymers of N-vinylformamide, vinyiamine and acrylamide, terpolymers of N-vinylformamide, vinyiamine and acrylate, terpolymers of N-vinylformamide, vin
- the molecular weight ( w ) of the functionalized vinylamine- containing base polymer can range from about 2,000 to about 1,000,000 Daltons, can be from about 4,000 to about 800,000 Daltons, can be from about from 10,000 to 500,000 Daltons, and may be from about 50,000 to about 400,000 Daltons.
- the molecular weight ( possibly>) of the graft copolymer can be in the range of from about 4,000 to about 2,000,000 Daltons, can be from about 6,000 to about 1,000,000 Daltons, can be from about 100,000 to about 700,000 Daltons, and may be from about 100,000 to 400,000 Daltons.
- a method of producing a graft copolymer comprising a vinylamine-containing base polymer in an aqueous medium and reacting the base polymer with vinyl monomers at a pH of from about 1.0 to about 4.0 and a temperature of from about 30°C to about 100°C for about 10 to 300 minutes, can be about 30 minutes to 150 minutes and may be from about 40 minutes to about 80 minutes.
- the functionalized vinylamine-containing base polymer is present in a reaction medium in an amount of ftom about 0.1% to about 20% active solids, can be from about 1% to about 15% active solids, can be from about 2% to about 10% active solids, and may be from about 3% to about 8% active solids.
- the graft copolymers of acrylamide and the functionalized vinylamine-containing base polymers of the present invention may undergo chemical self-crossl inking under various conditions, resulting in a change in physical and chemical properties to form a gel or a high viscosity, high molecular weight polymer.
- Typical examples are the transamidation of vinylamine with polyacrylamide and formation of polyelectrolyte of the amines with anionic moieties derived from amides.
- the graft copolymers of a vinyl monomer and a functionalized vinylamine- containing base polymer of the present invention can be used in papermaking as a dry strength additive to improve paper and paperboard dry strength, to accelerate drainage of the pulp fiber and to increase the retention of fines and fillers by the pulp fibers in the papermaking process.
- the present composition could be used as a retention aid, deposit control and/or fixative agent, coagulant in paper making processes, flocculant in waste water treatment, plasticizer, viscosity modifier, personal care additive, coating material, and slow releasing carriers for various industrial applications.
- the graft copolymers of acrylamide and the functionalized polyvinylamine of the present invention provided improved dry strength properties of paper products when compared with a polyacrylamide derivative such as glyoxalated polyacrylamide and commercial cationic starch. It was found that the graft copolymers of the invention were more effective at treatment levels from about 0.01 active wt. % to about 0.5 active wt. % based on the weight of the dry pulp relative to the glyoxalated polyacrylamide derivative.
- the paper products made with the composition of the present invention had lower permanent wet strength than those made with polyvinylamine and glyoxalated polyacrylamide.
- the graft copolymers of the present invention can be used in combination with other compositions or additives in order to improve the physical and application properties of the graft copolymer.
- the compositions or additives can be cationic, anionic, amphoteric, nonionic synthetic, or a natural polymer.
- the graft copolymers can be used together with a cationic starch or an amphoteric starch to improve the strength properties of paper products.
- the graft copolymers can be used in combination with an anionic polymer, such as a polyacrylic acid, a copolymer of acrylamide, an acrylic acid, or a carboxylmethyl cellulose.
- they could be used in combination with a cationic polymer such as crosslinked polyamidoamines,
- the graft copolymers can also be used in combination with, for example, polymeric aldehyde-functional compounds, such as glyoxalated polyacrylamides, aldehyde celluloses and aldehyde functional polysaccharides.
- Individual compositions or any combination of different compositions may be applied together with the graft polymers of the present invention, or may be applied sequentially before or after the application of the polymers.
- Individual compositions may be blended together with the polymers of the present invention to form a blended composition prior to use.
- the graft copolymers of the present invention can be used in combination with other additives in order to improve the physical and application properties of the graft copolymer.
- the additives can be aqueous dispersions such as those described in U.S. Pat. No. 5,938,937. These types of dispersions are commonly referred to as "brine dispersions.”
- U.S. Pat. No. 5,938,937 teaches that various combinations of low molecular weight highly cationic dispersion polymers and elevated inorganic salt content can be effective in producing a cationic aqueous dispersion polymer.
- Yet other aqueous dispersions are described in U.S. Pat. No.
- a dispersion of this type is generally composed of two different polymers: (1) A highly cationic dispersant polymer of a lower molecular weight (“dispersant polymer”), and (2) a less cationic polymer of a higher molecular weight that forms a discrete particle phase when synthesized under particular conditions ("discrete phase").
- Dispersant polymer A highly cationic dispersant polymer of a lower molecular weight
- discrete phase a less cationic polymer of a higher molecular weight that forms a discrete particle phase when synthesized under particular conditions.
- PerformTM P 2350 and PerformTM PK2320 are products available from Solenis LLC that are aqueous dispersions of a cationic amide-containing polymer with a low inorganic salt content.
- aqueous dispersions of a cationic amide- containing polymer can be blended with the vinylamine-containing graft copolymers of the present invention to form a composition that is not gelled nor is prohibitively high viscosity.
- the present invention blend provides enhanced drainage in addition to enhanced dry strength.
- the ratio of the aqueous dispersion of a cationic amide- containing polymer to the vinylamine-containing graft copolymers can be varied from 2:98 to about 40:60, can be from about 3:97 to about 30:70 and may be from about 5:95 to about 20: 80.
- the molar ratio of functionalized vinylamine base polymer to a vinyl monomer for graft polymerization can be varied from about 5:95 to about 40:60, can be from about 10:90 to about 30:70, and may be from about 5:95 to about 20:80.
- SEC size exclusion chromatography
- active polymer represents the total weight of the polymer as a percentage of a solution of all the monomers and modifying compounds used for making such a polymer on dry wt. basis.
- Brookfield viscosity (BV) was measured using a DV-II Viscometer (Brookfield Viscosity Lab, Middleboro, MA). A selected spindle (number 2) was attached to the instrument, which was set for a speed of 30 RPM. The reaction solution is prepared at a specific active polymer content (see Tables I, II and III). The Brookfield viscosity spindle was carefully inserted into the solution so as not to trap any air bubbles and then rotated at the above-mentioned speed for 3 minutes at 24°C. The units are given in centipoise (cps).
- the drainage activity of the invention was determined utilizing a modification of the Dynamic Drainage Analyzer, test equipment available from AB Akribi Kemikonsulter, Sundsvall, Sweden.
- the modification consists of substituting a mixing chamber and filtration medium with both smaller sample volume and cross-sectional area to the machine.
- a 250 milliliter (ml) sample volume at 0.3% consistency and a 47 millimeter (mm) cross-sectional filtration diameter (60-mesh screen) were used in these tests.
- the test device applies a 400 mbar vacuum to the bottom of the separation medium.
- the device electronically measures the time between the application of vacuum and the vacuum break point, i.e. the time at which the air/water interface passes through the thickening fiber mat. Results are given as drainage time with a lower drainage time is preferred.
- a drainage index (DI) can be calculated as the drainage time for the control system with no additives divided by the time it takes for the system with additives.
- the drainage testing was performed on paper pulp that was a blend of 25% unbleached softwood Kraft and 75% recycled medium with 50 parts-per-million (ppm) hardness, 25 ppm alkalinity, 2.5% GPC D15F oxidized starch (Grain Processing Corp., Muscatine, Iowa) and 2000 microSeimen per centimeter ⁇ S/cm) conductivity.
- the system pH was 7.0 and the pulp freeness was about 400 CSF for the Kraft fiber and 300 CSF for the recycled medium,
- Example 1 Graft copolymer of acrylamide and acrylamidopropyltrimethyl ammonium chloride (APTAC) functionalized polyvinylamine (PVAm/APTAC-g-PAM).
- ATAC acrylamidopropyltrimethyl ammonium chloride
- Acrylamidopropyltrimethylammonium chloride (APTAC) functionalized polyvinylamine was made using similar procedure described in Example 1 of US Patent No 7,902,312. As a typical example, a solution of polyvinylamine (100 grams (g), 14.0 % active solids) was added to a 1 liter (L) reaction flask and was adjusted to pH 11.3-11.5 using 50% NaOH. Acrylamidopropyltrimethylammonium chloride solution (1.63 grams (g) active solids) was added drop wise at 60 °C for 20 minutes. The resulting mixture was stirred at 60 °C for 2 hours to give an acrylamidopropyltrimethylammonium chloride functionalized polyvinylamine.
- ATAC Acrylamidopropyltrimethylammonium chloride
- a solution of the functionalized polyvinylamine prepared using above procedure was diluted to achieve desired target active solids in the range from 10% to 24% and adjusted to pH 3.6 by adding 37 % hydrochloric acid under stirring and purged with nitrogen gas for 30 minutes.
- Ferrous sulfate heptahydrate solution (2g, 1%) was added and the temperature of the resulting solution was raised to 60°C.
- Acrylamide (75.60g active solids) was drop wise added over 60 minutes under stirring while simultaneously adding 30.0g of hydrogen peroxide solution (5%) over a 90 minute time period.
- the reaction was held at 60°C to 65°C for 1 hour after hydrogen peroxide addition was completed.
- the reaction solution was then cooled to ambient temperature and the pH adjusted to 5.0 using sodium hydroxide (50% by wt).
- Examples 1-1 to 1-6 were compositions prepared as described in Example 1 using different molar percents of acrylamidopropyltrimethylammonium chloride (APTAC) to polyvinylamine and different molar ratios of the functionalized polyvinylamine to acrylamide.
- ATAC acrylamidopropyltrimethylammonium chloride
- Example 2 represents a general procedure for making the current copolymers via simultaneous addition of a monomer acrylamide and an initiator.
- a solution of a polyvinylamine as the base polymer for the graft polymerization was diluted to achieve desired target active solids in the range from 10% to 24% and adjusted to pH 3.6 by adding 37 % hydrochloric acid while stirring and purged with nitrogen gas for 30 minutes.
- Ferrous sulfate solution 300 ppm based on acrylamide
- An acrylamide was added drop wise over 60 minutes under stirring while simultaneously adding a hydrogen peroxide solution (0.5 w/w % based on acrylamide) over 90 minutes.
- the reaction was held at 70°C for 1 hour after the hydrogen peroxide addition was completed.
- the reaction solution was then cooled to ambient temperature and the pH of the solution was adjusted to 5.0 using sodium hydroxide (50 %).
- Examples 2-1 to 2-2 were the compositions prepared as described in Example 2 using different molar percent of polyvinylamine to acrylamide. These two compositions were also used as comparative examples to compare with the compositions from Example 1 for dry strength performance on paper sheets. Table II. Polyacrylamide graft polyvinylamine via pro
- Example 3 represents a one pot reaction procedure of making the current graft copolymers.
- a solution of polyvinylamine as the base polymer for the graft is a solution of polyvinylamine as the base polymer for the graft
- Examples 3-1 to 3-3 use the compositions prepared as described in Example 2, using different molar percents of polyvinylamine to acrylamide. The conditions and analytical results are summarized in Table III.
- Comparative Example 1 A blended composition of a polyacrylamide
- polyvinylamine at 80:20 wt/wt ratio based on polymer active.
- Example 4 illustrates the dry strength properties of paper sheets made with the graft copolymer of acrylamide and polyvinylamine and APT AC functionalized polyvinylamine of the above examples were compared with the dry strength properties of paper sheet made with a benchmark dry strength resin glyoxalated polyacrylamide (GPAM) (Hercobond ® 1000, from Ashland Incorporated, Wilmington, DE, USA).
- GPAM dry strength resin glyoxalated polyacrylamide
- the paper was made using a papermaking machine located at 500 Hercules d., Wilmington DE.
- the paper pulp was 70 % Quinessec hardwood bleached Kraft and 30 % Rayonier softwood bleached Kraft refined separately using Andritz double desk refiner to 500 ml CSF freeness and then mixed to produce a pulp with 100 ppm hardness and 50 ppm alkalinity.
- the system pH was 7.0 with the stock temperature at 50°C.
- the basis weight was 25 pounds per 3000 ft 2 .
- the graft copolymer prepared in the above examples and Hercobond® 1000 were added as dry strength agents to the wet end of the papermaking machine at the level of 0.4 weight % of polymer active versus dry paper pulp.
- Table IV compares several representative graft copolymers of the present invention with a glyoxalated polyacrylamide, Hercobond ® 1000. All the graft copolymers of acrylamide and the acrylamidopropyltrimethylammonium chloride (APTAC)
- fimctionalized polyvinylamine base polymers at different levels evaluated gave improved dry tensile relative to Hercobond ® 1000 at the equal active basis.
- the graft copolymers (Example 1-1 to 1-6) of the present invention also gave lower wet tensile than the glyoxalated polyacrylamide, Hercobond ® 1000.
- the graft copolymer compositions of the present invention also provided higher dry tensile than the graft copolymers of aciylamide and polyvinylamine base polymers that were not functionalized with APTAC but contained a similar amount of primary amine from polyvinylamine at 15-20 mole % (Examples 2-1, 2-2 and 3-1).
- the graft copolymer with the base polyvinylamine not being functionalized by APTAC (Example 3-1) had higher dry tensile than (107.5 % vs. 98.8 %) Comparative Example 1, was prepared by blending a polyacrylamide with polyvinylamine at the same active solids basis.
- EXAMPLE 5 Table V, demonstrates that blending a small amount of cationic aqueous dispersion polymer (PerformTM PK 2320) into a PVAm/APTAC-g-PAM polymer solution results in a product with surprisingly enhanced drainage (examples 5-2, 5-3 and 5-4 as compared to 5-1 with no cationic dispersion addition).
- Tables VI and VII contain comparative examples of Polyacrylamide graft APTAC functionalized polyvinylamine (PVAm/APTAC-g-PAM) polymers combined with co- additives like bentonite (Bentolite H available from BYK Additives Inc., Gonzales, TX) and colloidal silica (Perform ® 9025 available from Solenis, LLC, Wilmington, DE) which are commonly used inorganic particulate drainage aids in the paper industry.
- Table VIII contains comparative examples of PVAm/APTAC-g-PAM polymers with added cationic dispersants, coagulants, or fiocculants such as PerForm® PC 8229,
- Prestafix ® PC125, and Prestafix ® PC 1229 available from Solenis, LLC, Wilmington, DE.
- Table VI shows only a small improvement when bentonite is added to the stock with PVAm/APTAC-g-PAM polymers; unlike the large drainage improvements demonstrated in Table V. It was not possible to make a stable single product blend with silica because the colloidal silica readily precipitated out in the presence of the polymer solutions.
- Table VII represents the drainage index for co-additive compositions of PVAm/APTAC-g-PAM polymers and colloidal silica. The DI is reduced with added silica.
- Table VIII demonstrates that alternative fixatives, coagulants, and fiocculants do not provide the synergistic drainage performance of adding the PVAm/APTAC-g-PAM polymers with a cationic aqueous dispersions as shown in Table 5.
- Table VI Polyacrylamide graft APTAC functionahzed polyvinylamine with Beiitonite Co-Additive
- Example 9 The results shown in Table IX, demonstrates the good gelation stability of the polyacrylamide graft iunctionalized vinylamine polymer (PVAm/APTAC- g-PAM) blended with a cationic amide-containing aqueous dispersion, such as, PK2320.
- PK2320 To form the blended single product, the PK2320 dispersion was slowly mixed into the polyvinylamine polymer solution at the wt% active listed in the Table.
- PK2320 at 28.7% polymer actives was blended with 91.8 g PVAm/APTAC-g-PAM polymer solution at 10.3%> active to form the blend wherein the w% active P 2320 is 20% of the total active polymer in solution.
Abstract
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AU2015247996A AU2015247996B2 (en) | 2014-04-16 | 2015-04-10 | Modified vinylamine containing polymers and their use in papermaking |
CA2945748A CA2945748C (en) | 2014-04-16 | 2015-04-10 | Modified vinylamine containing polymers and their use in papermaking |
EP15719353.3A EP3132092B1 (en) | 2014-04-16 | 2015-04-10 | Modified vinylamine containing polymers and their use in papermaking |
BR112016023789-7A BR112016023789B1 (en) | 2014-04-16 | 2015-04-10 | Graft copolymer composition of a vinyl monomer and a functionalized vinylamine-containing base polymer and process for manufacturing a graft copolymer composition |
MX2016013385A MX2016013385A (en) | 2014-04-16 | 2015-04-10 | Modified vinylamine containing polymers and their use in papermaking. |
RU2016144713A RU2678672C2 (en) | 2014-04-16 | 2015-04-10 | Modified vinylamine containing polymers and their application in manufacturing of paper |
ES15719353T ES2759450T3 (en) | 2014-04-16 | 2015-04-10 | Modified polymers containing vinylamine and their use in papermaking |
KR1020167028376A KR102386090B1 (en) | 2014-04-16 | 2015-04-10 | Modified vinylamine containing polymers and their use in papermaking |
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US20150299961A1 (en) | 2015-10-22 |
US20170233949A1 (en) | 2017-08-17 |
CA2945748C (en) | 2019-07-09 |
CL2016002626A1 (en) | 2017-02-03 |
ZA201607874B (en) | 2018-11-28 |
PT3132092T (en) | 2019-12-18 |
AU2015247996A1 (en) | 2016-10-13 |
BR112016023789B1 (en) | 2022-01-25 |
BR112016023789A2 (en) | 2021-08-03 |
EP3132092A1 (en) | 2017-02-22 |
MX2016013385A (en) | 2017-02-15 |
US9879380B2 (en) | 2018-01-30 |
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